CN112117459A - Polymer electrolyte lithium cell with formation aid material - Google Patents

Polymer electrolyte lithium cell with formation aid material Download PDF

Info

Publication number
CN112117459A
CN112117459A CN202010558906.0A CN202010558906A CN112117459A CN 112117459 A CN112117459 A CN 112117459A CN 202010558906 A CN202010558906 A CN 202010558906A CN 112117459 A CN112117459 A CN 112117459A
Authority
CN
China
Prior art keywords
lithium
polymer electrolyte
cathode
fluoride
cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010558906.0A
Other languages
Chinese (zh)
Inventor
U·伯纳
U·索特
E·克劳斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of CN112117459A publication Critical patent/CN112117459A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a polymer electrolyte lithium cell (10) comprising an anode (11), a cathode (12) and a separator (13) arranged between the anode (11) and the cathode (12). Here, the anode (11) comprises metallic lithium. The separator (13) and/or the cathode (12) comprise at least one polymer electrolyte. The cathode (12) comprises at least one lithium intercalation material and/or lithium intercalation material having a redox potential with respect to lithium of ≥ 2.5V. In order to provide a polymer electrolyte lithium cell with reduced interfacial resistance and improved capacity, the cathode (12) further comprises at least one formation aid material capable of being reduced and capable of reacting with lithium at a potential in the range between 2.5V and 1.5V relative to lithium. In addition, the invention also relates to such polymer electrolyte lithium batteries and methods of formation.

Description

Polymer electrolyte lithium cell with formation aid material
Technical Field
The invention relates to a polymer electrolyte lithium cell, a polymer electrolyte lithium battery and a method of forming.
Background
Electrical energy can be stored by means of lithium cells and lithium batteries, which convert chemical reaction energy into electrical energy. The battery may comprise one or more cells, and may be a primary or secondary battery. Here, the primary battery can be used only once, and the secondary battery (also referred to as a secondary battery) can be recharged.
Lithium cells, such as lithium ion cells, are used in particular in secondary batteries or accumulators and have a cathode (also referred to as positive electrode) and an anode (also referred to as negative electrode) and a separator arranged between the anode and the cathode. Here, the cathode and anode each comprise an active material that is typically attached to a current collector, respectively.
In conventional lithium ion cells, metal oxides are often used as cathode active materials, while graphite, amorphous carbon (e.g., so-called hard carbon), silicon, and/or lithium titanate are used as anode active materials. At the end of production, conventional lithium ion cells are typically filled with a liquid electrolyte. In order to produce protective layers, so-called SEI layers (solid electrolyte interface/interphase layers), in a targeted manner on the anode and optionally also on the cathode, conventional lithium-ion cells and batteries are generally subjected to a formation step in which a specific potential is applied to the anode and the cathode in order to advantageously oxidize and/or reduce specific substances in the liquid electrolyte. In this way also impurities can be removed. After formation, the generated gas may be removed from the cell and the battery hermetically sealed. Such a process is described, for example, in the US2018/034097a1 publication.
The polymer electrolyte lithium cell comprises at least one polymer electrolyte. Here, the cathode and/or the separator may comprise the at least one polymer electrolyte. In such a case, one type of formation, also referred to as pre-discharge, may also be performed. The formation is usually carried out here by a stepwise or linear reduction of the potential at the cathode to below 1.5V. Impurities, such as water and/or solvent residues, at the cathode can thereby be reduced to gaseous substances and removed in this way. Here, the reduction reaction at the cathode consumes lithium, which is oxidized to lithium ions (Li) by the oxidation from metallic lithium+) And is detached from the anode. In the case of anodes containing metallic lithium, for example lithium metal anodes in the form of lithium metal foils, the uppermost layer of the anode can be detached, so that a "fresh" metal surface is formed. However, if the potential is too low, adverse reactions may occur in the cell.
Publication US2018/048018a1 relates to the application of force to an electrochemical cell.
Disclosure of Invention
The subject of the invention is a polymer electrolyte lithium cell, in particular a polymer electrolyte lithium ion cell, comprising an anode, a cathode and a separator arranged between the anode and the cathode. Here, the anode includes metallic lithium. The separator and/or the cathode here comprise at least one polymer electrolyte. The cathode here comprises at least one lithium intercalation and/or insertion material having a redox potential of ≧ 2.5V, in particular with respect to metallic lithium.
The cathode here also comprises, in particular, at least one formation auxiliary material, which can be used, in particular, with respect to lithium metal (Li/Li)+) Is reduced and is capable of reacting with lithium, e.g. reversibly or irreversibly, at a potential in the range between 2.5V and 1.5V.
Due to this formation aid material, the surface of the anode can advantageously be cleaned and, for example, a "fresh" metal surface can be produced without having to apply a potential on the cathode which is so low that, in particular, undesirable reactions of the at least one polymer electrolyte, for example of polyethylene oxide (PEO), do not occur in the cell.
This advantageously makes it possible to avoid undesirable reactions in the cell, for example irreversible reactions of at least one polymer electrolyte, for example irreversible reactions of polyethylene oxide.
In this way, the at least one formation aid material is able to release lithium even at potentials ≧ 1.5V in an amount which is sufficiently high for continued improvement of the electrochemical performance of the battery. Without the addition of the at least one formation aid material, a similarly high detachment rate could hitherto only be achieved at relatively low potentials, in particular potentials below about 1.3V, at which conventional polymer electrolytes, for example polyethylene oxide, also react.
The specific cleaning of the anode surface, in particular, advantageously reduces the interfacial resistance (Grenzfl ä chenwindstand) and in this way improves the cell performance.
In summary, polymer electrolyte lithium cells with reduced interfacial resistance and improved capacity may thus be provided.
The at least one formation aid material is preferably selected such that no or only very small amounts of gaseous substances are produced upon reduction thereof.
Within the scope of an embodiment, the at least one formation aid material is in particular lithium metal (Li/Li)+) Can be reversibly reduced and/or redox active at a potential in the range of 2.5V to 1.5V. Due to the at least one forming aid material being at 2.5V>U>The potential range of between 1.5V, which can be reversibly reduced and/or redox-active, advantageously allows the amount of lithium on the anode, which is pre-stored for the formation, in particular pre-discharge, to be restored during the subsequent charging process. It is therefore not necessary to maintain an additional lithium excess on the anode for the formation, in particular the predischarge, which excess exceeds the usual lithium excess for ensuring cell cycling stability. Reversible reduction of the at least one formation-assisting materialThe protogenic and/or redox activity furthermore enables the at least one formation aid material to serve as deep discharge protection for the at least one lithium intercalation and/or intercalation material.
Within the scope of a further embodiment, the at least one formation aid material comprises or is at least one conversion material. The at least one formation aid material may in particular comprise at least one conversion material that is processable in the cathode in the charged state. Advantageously, the conversion material may be in particular lithium metal (Li/Li), in particular+) Is reversibly reducible and redox active at potentials in the range between 2.5V and 1.5V.
In another embodiment, the at least one formation aid material, in particular the conversion material, comprises or is sulphur and/or selenium and/or tellurium and/or at least one fluoride and/or at least one chloride. These substances may be advantageous as forming aid materials or conversion materials.
In one embodiment of this embodiment, the at least one formation aid material, in particular the conversion material, comprises either elemental sulfur and/or at least one sulfur compound and/or elemental selenium and/or at least one selenium compound and/or elemental tellurium and/or at least one tellurium compound and/or at least one metal fluoride, in particular at least one transition metal fluoride and/or at least one main group metal fluoride, in particular a fifth main group metal fluoride, and/or at least one metal chloride, in particular at least one transition metal chloride. These materials can be advantageously utilized.
In a particular embodiment of this embodiment, the at least one auxiliary forming material, in particular the conversion material, comprises or is elemental sulfur and/or at least one sulfur-polymer complex, in particular at least one polyacrylonitrile-sulfur complex, such as SPAN or PAN-S, and/or elemental selenium and/or at least one selenium compound having covalently bonded selenium chains, for example selenium side chains, and/or elemental tellurium and/or at least one tellurium compound having covalently bonded tellurium chains, for example tellurium side chains, and/or at least one iron fluoride, for example iron (II) fluoride (FeF)2) And/or iron fluoride(s) (iii)III）（FeF3) And/or vanadium fluorides, e.g. vanadium (III) fluoride (VF)3) And/or manganese fluorides, e.g. manganese (III) fluoride (MnF)3) And/or titanium fluorides, e.g. titanium (III) fluoride (TiF)3) And/or bismuth fluorides, e.g. bismuth (III) fluoride (BiF)3) And/or copper fluoride, e.g. copper (II) fluoride (CuF)2) And/or at least one manganese chloride, e.g. manganese (II) chloride (MnCl)2) And/or silver chloride, e.g. silver (I) chloride (AgCl), and/or copper chloride, e.g. copper (II) chloride (CuCl)2）。
The cathode may in particular comprise a cathode material, which may also be referred to as cathode mixture.
In another embodiment, the cathode material comprises at least one polymer electrolyte.
In another embodiment, the cathode material comprises at least one lithium intercalation and/or intercalating material and at least one forming aid material.
Further, the cathode may include a cathode current collector.
In another embodiment, the cathode current collector is provided with a coating comprising said at least one forming aid material. The cathode current collector may in particular be provided with a coating comprising at least one forming aid on the side facing the cathode material.
Within the scope of a further embodiment, the at least one lithium intercalation and/or insertion material comprises or is at least one lithium iron phosphate (LFP) and/or lithium nickel oxide and/or lithium nickel cobalt oxide and/or lithium nickel manganese oxide, in particular lithium nickel cobalt manganese oxide (NCM), and/or lithium cobalt aluminum oxide (NCA) and/or at least one lithium transition metal spinel, in particular lithium manganese spinel. Such lithium intercalation and/or insertion materials may advantageously be used with respect to lithium (Li/Li) in particular metals+) Has redox activity at a potential of 2.5V or more.
Within the scope of another embodiment, the anode is a lithium metal anode. A lithium metal anode is understood to mean, in particular, an anode made of metallic lithium or lithium metal. For example, an anode, particularly a lithium metal anode, may be constructed in the form of a lithium metal foil.
Within the scope of a further embodiment, the at least one polymer electrolyte of the separator and/or the at least one polymer electrolyte of the cathode, in particular of the cathode material, comprises at least one polyalkylene oxide, for example polyethylene oxide.
The at least one formation aid may be detected, for example, using classical analytical chemistry methods, such as mass spectrometry, chromatography, and/or elemental analysis.
With regard to further technical features and advantages of the cell according to the invention, explicit reference is made here to the explanations made in connection with the battery according to the invention, the method according to the invention and the explanations with reference to the figures and the drawings.
Another subject of the invention is a polymer electrolyte lithium battery, in particular a polymer electrolyte lithium ion battery, comprising at least one cell according to the invention. A polymer electrolyte lithium battery may in particular comprise a plurality of cells according to the invention.
The battery cells and/or batteries according to the invention can be used, for example, in the field of applications such as electric vehicles, for example in motor vehicles, in particular Electric Vehicles (EV) and/or Hybrid Electric Vehicles (HEV) and/or plug-in hybrid electric vehicles (PHEV;), and/or in telecommunications electronics and/or in domestic appliances and/or tools and/or gardening tools.
With regard to further features and advantages of the battery according to the invention, explicit reference is made here to the explanations made in connection with the cell according to the invention, the method according to the invention and the figures and the description of the figures.
The invention also relates to a method for forming a polymer electrolyte lithium cell and/or battery according to the invention, wherein the cathode potential is reduced stepwise or linearly to ≧ 1.5V, particularly before cycling. The formation can be carried out in particular at temperatures of > 70 deg.C, for example > 75 deg.C, for example > 80 deg.C. For example, the cell can be formed in a sealed state or in an open state. In particular, the cell can be formed in a sealed state.
With regard to further features and advantages of the method according to the invention, explicit reference is made here to the explanations made in connection with the cell according to the invention, the battery according to the invention and the figures and the figure descriptions.
Further advantages and advantageous configurations of the subject matter according to the invention are illustrated in the accompanying drawings and explained in the following description. It should be noted herein that the drawings are merely descriptive of features and are not intended to limit the invention in any way.
Drawings
FIG. 1: a schematic cross-sectional view of one embodiment of a polymer electrolyte lithium battery according to the present invention;
FIG. 2: a graph illustrating the relationship between lithium desorption and final voltage when a cell is formed;
FIG. 3: a graph illustrating the relationship between lithium desorption and transition resistance or capacity and time when a cell is formed; and
FIG. 4: a graph illustrating the interfacial resistance of the formed cells.
Detailed Description
Fig. 1 shows an embodiment of a polymer electrolyte lithium cell 10 at the beginning of formation, in particular pre-discharge. Fig. 1 shows that the battery cell 10 includes an anode 11, a cathode 12, and a separator 13 disposed between the anode 11 and the cathode 12.
Here, the anode 11 contains metallic lithium as an anode material 11 a. The anode 11 may be a lithium metal anode, for example, in the form of a lithium metal foil. The dashed rectangle identified by reference numeral 11b herein indicates that the anode 11 may also include an anode current collector 11 b.
Here, the cathode 12 includes a cathode material 12 a. The cathode material 12a may comprise, inter alia, at least one lithium intercalation and/or insertion material with respect to lithium (Li/Li)+) Has an oxidation-reduction potential of more than or equal to 2.5V. The at least one lithium intercalation and/or insertion material may comprise or be lithium iron phosphate (LFP), for example. Additionally, cathode material 12a may include at least one polymer electrolyte, such as polyethylene oxide.
Here, the dashed rectangle identified by reference numeral 12b indicates that the cathode 12 may further include a cathode current collector 12 b. Here, the dashed rectangle identified by reference numeral 12c indicates that the cathode 12 may further include a coating 12c applied to the cathode current collector 12 b. Fig. 1 shows that the cathode current collector 12b can in particular be provided with a coating 12c on the side facing the cathode material 12 a.
Separator 13 may also include at least one polymer electrolyte, such as polyethylene oxide. Here, the at least one polymer electrolyte of the separator 13 may be the same as or different from the at least one polymer electrolyte of the cathode 12, particularly of the cathode material 12 a.
Cathode 12 also includes at least one formation aid material that is compatible with lithium (Li/Li)+) Is in the range of 2.5V to 1.5V, can, for example, be reduced reversibly or irreversibly and can react with lithium. The at least one formation aid material may be in particular lithium (Li/Li) in this case+) Is reversibly reduced and/or redox in the range of 2.5V to 1.5V. The at least one formation aid material may especially comprise a conversion material, such as sulphur and/or selenium and/or tellurium and/or at least one fluoride and/or at least one chloride.
Within the scope of one configuration, cathode material 12a includes at least one lithium intercalation and/or intercalation material and at least one formation aid material.
Within the scope of another alternative or additional configuration, the coating 12c on the cathode current collector 12b includes at least one forming aid material.
Such a cell 10 may have a cell voltage of about 3.25V in a newly assembled state. During the formation, in particular the pre-discharge, of the new cell 10, the potential at the cathode 12 is reduced, in particular linearly or stepwise, to ≧ 1.5V before cycling. Here, during formation, different reactions may take place at a specific potential at the cathode 12, for example at<At a potential of 2.5V water reduction and/or<Solvent such as cyclohexanone at a potential of 1.8V. The more these reactions proceed at the cathode 12, the more lithium is simultaneously removed from the anode 11. Arrow e-The direction of the current flow during the formation, in particular the pre-discharge, is identified here.
Fig. 2 shows the lithium detachment process in micrometers measured during a stepwise conventional formation, in particular a pre-discharge, in a lithium/iron phosphate lithium battery (Li/LFP) without formation of auxiliary material, as a function of the final voltage in volts.
Fig. 2 shows that the conventional formation usually ends when 1.1V is reached. Lithium detachment of up to about 0.5 μm at the anode can thereby be achieved.
In fig. 3, the lithium detachment in micrometers (y-axis on the right) and the transition resistance or the associated capacity in ampere-hours (y-axis on the left) relative to the time in hours (x-axis) are shown at different temperatures, i.e. 45 ℃ and 80 ℃ during approximately seven hours of formation, in particular pre-discharge, and with the same potential drop, in particular in four phases.
Fig. 3 shows that 0.7 to 0.5 microns of lithium are released at 80 c with the cell open and closed, but only about 0.3 microns at 45 c.
Fig. 3 also shows that the more lithium is removed, the lower the transition resistance or the higher the associated capacity. By forming at 80 ℃, a significantly lower transition resistance or a significantly higher capacity can be achieved with both open and closed cells than at 45 ℃. The best results are achieved here by forming the closed cell at 80 ℃.
Fig. 4 shows that the transition resistance (ASR) of the cells formed at 80 ℃ in the closed and open state is significantly lower than that of the cells formed at 45 ℃ and the untreated cells (grey bars).

Claims (14)

1. A polymer electrolyte lithium cell (10) comprising an anode (11), a cathode (12) and a separator (13) arranged between the anode (11) and the cathode (12),
wherein the anode (11) comprises metallic lithium,
wherein the separator (13) and/or the cathode (12) comprise at least one polymer electrolyte, and
wherein the cathode (12) comprises at least one lithium intercalation material and/or lithium insertion material having a redox potential ≥ 2.5V with respect to lithium,
wherein the cathode (12) further comprises at least one formation aid material which is reducible at a potential in the range between 2.5V and 1.5V relative to lithium and which is capable of reacting with lithium.
2. The polymer electrolyte lithium cell (10) according to claim 1, wherein the at least one formation assisting material is reversibly reducible and/or redox active at a potential in the range between 2.5V and 1.5V relative to lithium.
3. The polymer electrolyte lithium cell (10) according to claim 1 or 2, wherein the at least one formation aid material comprises or is at least one conversion material.
4. The polymer electrolyte lithium cell (10) according to any of claims 1 to 3, wherein the at least one formation aid material, in particular the at least one conversion material, comprises sulfur and/or selenium and/or tellurium and/or at least one fluoride and/or at least one chloride.
5. The polymer electrolyte lithium cell (10) according to any of claims 1 to 4, wherein the at least one forming auxiliary material, in particular the at least one conversion material, comprises elemental sulphur and/or at least one sulphur compound and/or elemental selenium and/or at least one selenium compound and/or elemental tellurium and/or at least one tellurium compound and/or at least one metal fluoride, in particular at least one transition metal fluoride and/or at least one main group metal fluoride, in particular a fifth main group metal fluoride, and/or at least one metal chloride, in particular at least one transition metal chloride.
6. The polymer electrolyte lithium cell (10) according to any one of claims 1 to 5, wherein the at least one formation aid material comprises elemental sulfur and/or at least one sulfur-polymer-composite, in particular at least one polyacrylonitrile-sulfur-composite, and/or elemental selenium and/or at least one selenium compound having covalently bonded selenium chains and/or elemental tellurium and/or at least one tellurium compound having covalently bonded tellurium chains and/or at least one iron fluoride, in particular iron (II) fluoride and/or iron (III) fluoride, and/or vanadium fluoride, in particular vanadium (III) fluoride, and/or manganese fluoride, in particular manganese (III) fluoride, and/or titanium fluoride, in particular titanium (III) fluoride, and/or bismuth fluoride, in particular bismuth (III) fluoride, and/or copper fluoride, in particular copper (II) fluoride, and/or at least one manganese chloride, in particular manganese (II) chloride, and/or silver chloride, in particular silver (I) chloride, and/or copper chloride, in particular copper (II) chloride.
7. The polymer electrolyte lithium cell (10) according to any one of claims 1 to 6, wherein the cathode (12) comprises a cathode material (12 a), wherein the cathode material (12 a) comprises the at least one lithium intercalation material and/or lithium intercalation material and the at least one formation aid material.
8. The polymer electrolyte lithium cell (10) according to any of claims 1 to 7, wherein the cathode (12) comprises a cathode current collector (12 b), wherein the cathode current collector (12 b) is provided with a coating (12 c) comprising the at least one forming aid material.
9. The polymer electrolyte lithium cell (10) according to any of claims 1 to 8, wherein the cathode material (12 a) comprises at least one polymer electrolyte.
10. The polymer electrolyte lithium cell (10) according to any of claims 1 to 9, wherein the at least one lithium intercalation material and/or lithium intercalation material comprises or is at least one lithium iron phosphate and/or lithium nickel oxide and/or lithium nickel cobalt oxide and/or lithium nickel manganese oxide, in particular lithium nickel cobalt manganese oxide, and/or lithium cobalt aluminum oxide and/or at least one lithium transition metal spinel, in particular lithium manganese spinel.
11. The polymer electrolyte lithium cell (10) according to any of claims 1 to 10, wherein the anode (11) is a lithium metal anode, in particular a lithium metal foil.
12. The polymer electrolyte lithium cell (10) according to any of claims 1 to 11, wherein at least one polymer electrolyte of the separator (13) and/or the cathode (12), in particular the at least one polymer electrolyte of the cathode material (12 a), comprises at least one polyalkylene oxide, in particular polyethylene oxide.
13. Polymer electrolyte lithium battery comprising at least one cell according to one of claims 1 to 12.
14. Method for forming a polymer electrolyte lithium cell (10) and/or a polymer electrolyte lithium battery according to any one of claims 1 to 13, wherein the potential on the cathode (12) is reduced stepwise or linearly to ≥ 1.5V, in particular at a temperature ≥ 70 ℃.
CN202010558906.0A 2019-06-19 2020-06-18 Polymer electrolyte lithium cell with formation aid material Pending CN112117459A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019208911.9A DE102019208911A1 (en) 2019-06-19 2019-06-19 Polymer electrolyte lithium cell with auxiliary formation material
DE102019208911.9 2019-06-19

Publications (1)

Publication Number Publication Date
CN112117459A true CN112117459A (en) 2020-12-22

Family

ID=70918219

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010558906.0A Pending CN112117459A (en) 2019-06-19 2020-06-18 Polymer electrolyte lithium cell with formation aid material

Country Status (3)

Country Link
EP (1) EP3754765A1 (en)
CN (1) CN112117459A (en)
DE (1) DE102019208911A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104641503A (en) * 2012-04-26 2015-05-20 罗克伍德锂有限责任公司 1.5-3V lithium batteries with overcharge protection
DE102015210749A1 (en) * 2015-06-12 2016-12-15 Robert Bosch Gmbh Lithium-sulfur cell cathodic additives for quasi-constant voltage step
DE102016225273A1 (en) * 2016-12-16 2018-06-21 Robert Bosch Gmbh SIC-MOF-electrolyte
CN108352565A (en) * 2015-06-04 2018-07-31 离子材料公司 Lithium metal battery with solid polymer electrolyte

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100502896B1 (en) * 2003-04-16 2005-07-22 삼성에스디아이 주식회사 Current collector for positive electrode of lithium-sulfur battery, positive electrode for lithium-sulfur battery comprising same and lithium-sulfur battery comprising same
US9105938B2 (en) * 2008-08-05 2015-08-11 Sion Power Corporation Application of force in electrochemical cells
KR101889675B1 (en) * 2015-02-16 2018-08-17 닛산 지도우샤 가부시키가이샤 Manufacturing Method of Lithium Ion Secondary Battery
US10312523B2 (en) * 2016-02-25 2019-06-04 Tdk Corporation Lithium ion secondary battery
CN109831926A (en) * 2016-06-30 2019-05-31 罗伯特·博世有限公司 The method for forming battery
US10770721B2 (en) * 2017-04-10 2020-09-08 Global Graphene Group, Inc. Lithium metal secondary battery containing anode-protecting polymer layer and manufacturing method
US10497927B2 (en) * 2017-08-31 2019-12-03 GM Global Technology Operations LLC Methods of applying self-forming artificial solid electrolyte interface (SEI) layer to stabilize cycle stability of electrodes in lithium batteries
US20190097275A1 (en) * 2017-09-26 2019-03-28 David Mitlin Selenium impregnated materials as free-standing electrodes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104641503A (en) * 2012-04-26 2015-05-20 罗克伍德锂有限责任公司 1.5-3V lithium batteries with overcharge protection
CN108352565A (en) * 2015-06-04 2018-07-31 离子材料公司 Lithium metal battery with solid polymer electrolyte
DE102015210749A1 (en) * 2015-06-12 2016-12-15 Robert Bosch Gmbh Lithium-sulfur cell cathodic additives for quasi-constant voltage step
DE102016225273A1 (en) * 2016-12-16 2018-06-21 Robert Bosch Gmbh SIC-MOF-electrolyte

Also Published As

Publication number Publication date
DE102019208911A1 (en) 2020-12-24
EP3754765A1 (en) 2020-12-23

Similar Documents

Publication Publication Date Title
JP6334720B2 (en) Cyanometalate positive electrode battery and manufacturing method
US10020506B2 (en) Active material for a cathode of a battery cell, cathode, and battery cell
KR102043247B1 (en) Rechargeable electrochemical cell
JP6469725B2 (en) Galvanic element and manufacturing method thereof
US20190214675A1 (en) Method of Forming a Secondary Battery
CN112670559A (en) Solid electrolyte and method for preparing the same
US20180138497A1 (en) Na-doped and nb-, w-, and/or mo-doped he-ncm
US9406960B2 (en) Energy storage systems having an electrode comprising LixSy
US10483586B2 (en) All-solid-state battery using sodium ion intercalation cathode with Li/Na exchanging layer
CN106104861B (en) Electrode for lithium battery
CN113314698A (en) Composite reference electrode substrate and associated methods
US20220359875A1 (en) Composite Interlayer For Lithium Metal Based Solid State Batteries And The Method Of Making The Same
CN112117459A (en) Polymer electrolyte lithium cell with formation aid material
CN117154341A (en) Polymer barrier for solid state battery
US20170033363A1 (en) Method for producing an electrode of a lithium-ion battery
JP6301931B2 (en) Battery charge transfer mechanism
US20170324111A1 (en) Electrode for a battery cell and a battery cell
CN114388883A (en) Solid state bipolar battery comprising ionic gel
US20180083315A1 (en) Coated Cathode Active Material for Engineered Solid-State Battery Interfaces
US20230299342A1 (en) Thin Solid-State Electrolyte Having High Ionic Conductivity
US10811732B1 (en) Pre-lithiation for batteries having si-anodes
KR102463421B1 (en) A catalyst for an anode of a lithium-air battery, and a lithium-air battery including the same
CN116565304A (en) Lithiation additive for solid state battery comprising gel electrolyte
CN116505082A (en) Method for reducing interface resistance in solid-state battery
CN117438639A (en) Free standing thin electrolyte layer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination